US3244727A - Pesticidally active halogenated tricyclic sultones and their preparation - Google Patents

Pesticidally active halogenated tricyclic sultones and their preparation Download PDF

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US3244727A
US3244727A US143539A US14353961A US3244727A US 3244727 A US3244727 A US 3244727A US 143539 A US143539 A US 143539A US 14353961 A US14353961 A US 14353961A US 3244727 A US3244727 A US 3244727A
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Edward D Weil
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Occidental Chemical Corp
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Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 1, 1982. Assignors: HOOKER CHEMICALS & PLASTICS CORP.
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D327/00Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06Six-membered rings
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/32Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings

Description

United States Patent 3,244,727 PESTICIDALLY ACTIVE HALOGEN-ATED TRICY- CLIC SULTONES AND THEIR "PREPARATION Edward D. Weil, Lewiston, N.Y., assignor to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York No Drawing. Filed Oct. 9, 1961,.Ser. No. 143,539 '6 Claims. (Cl. 260-327) This invention describes certain novel biocidal tricyclic sultones and methods for their use and preparation.

More particularly, this invention relates to hexahalo tri-unsaturated tricyclic sultones having utility as pesticides, particularly as fungicides and miticidesyas pesticidal intermediates and as useful chemical intermediates generally. These compositions have the structure:

OX: SIO X l ci wherein X is a member of the group consisting of the halogens. The X substituents may be the same or different halogens.

The compounds having preferably all chlorine or all bromine substituted on the left hand bicycli'c moiety are the preferred compositions of this invention because of ease of synthesis, the availability'of starting materials and the cost of manufacture. For the sake of brevity, the hexachloro composition of this invention is referred to as C9H203C15S.

The hexahalo compositions of this invention are-crystalline solids having sharp melting points. The hexachloro product is a colorless crystalline solid of M.P. 130'degrees Centigrade. This chlorinated product is stable up to temperatures of about 230 degrees centigrade at which temperature it breaks down with evolution of S0 It is substantially insoluble in water and is soluble'in most organic solvents including aromatic hydrocarbons such as xylene, chlorinated hydrocarbons, alcohols, ketones, esters, and ethers, and slightly soluble in alkanes.

As indicated above, the compositionsof this invention exhibit pesticidal activity, and are particularly outstandng as fungicides. They also .possess certain insecticidal activity such as toxicity toward mites and the like, and are active also against bacteria and marine fouling organisms. In addition, the compositions of thisinvention,':their halogenation products, rthermal decomposition products, hydrogenation products, adducts and products in which the sultone ring has been cleaved or opened. by nucleophilic reagents are useful as pesticides, as intermediates for preparing pesticides, or-for organic synthesis generally.

In addition to their major advantages of biocid'al activity and their availability as biocidal intermediates and chemical intermediates, this invention in its compositon aspect offers additional major. advantages.

For example, these compositions due to their unique structure, stability and solubility in a variety of organic solvents lend themselves to formulation in diverse form-s ranging from the simple to the complex. The invention compositions may be utilized as biocides, particularly as fungicides and miticides in the pure form or as reaction crudes. Where they are to beused as intermediates, the purified product is often both necessary and desirable.

The pesticidal preparations are conveniently made up as liquid or as solid formulations. Examples of solid formulations are dust-s, wettable powders, granules and pellets. Each of these may contain one 'or more' of the invention compositions combined with .a solid carrier or extender, ordinarily a non-reacting or inert substance such as sand, clays, tales, sawdust, flours, alkaline earth-carbonates, oxides, phosphates, and the like as well as diatomacious earths, 'micas and similar suitable materials.

'Where liquid formulations are desirable, liquid extenders, diluents or carriers of a non-reactive nature are utilized. Examples of such materials are aliphatic alcohols, chlorocarbons, ketones and g'lycols, aromatic hydrocalrl'bons, petroleum fractions and distillates among many ot ers.

Where it is desired to-use the aforementioned wettable powders, or liquid formulations either emulsified, dispersed or suspended in Water or'ot-her fluid, one or more of .a class of materials herein referred to as adjuvants may be incorporated into the powder, dust, or liquid formulation. These materials "comprise surface active agents, detergents, wetting agents,.-solubilizin'g agents, stabilizers, dispersing agents, suspending agents, emulsifying agents, Spreaders, stickers, and conditioning agents generally. These materials through their modifying characteristics facilitate handling and application, and not infrequently, enhance or potentiate the compositions of this invention in their pesticidal activity by mechanisms frequently not well understood.

A satisfactory .but not exhaustive list of these substances appears among other places in Soap and Chemical Specialities, volume 31, No. 7, page 61; N0. 8, pages 48-61; No. '9, pages 52-67, and No. .10, :pages 38-67 (1955 Also, see Bulletin 'E-607 -of the Bureau of Entomology and Plant Quarantine of the United States Department of Agriculture.

.An additional. advantage of the inventive compositions is their compatibility with a variety of biocidal materials. For example, .it-rnay frequently be convenient tocornbine one or more compositions of this invention with one or more adjuvants "and carriers with insecticidal materials such as chlordane, benzene hexachlorides, DDT, DDD, the insecticidal carbamates, polychlorinated iterpenes, the parathions, methoxychlor, insecticidal phosphates, phosphorothioates, and phosphorodithioates, with other fungicides such as sulfur, quinones, 'dodecylguanidine, the metal dimethyldithiooarbamates, N-trihalomethylthio-4- cyclohexene l,2-dicarboximide, N-(trichloromethylthio) phthalimide, heptadecylimidazoline, dinitrocapryl orotonate and various fungicidal zinc, iron, nickel, manganese, copper, lead and mercury salts.

In its process aspects, the present invention offers several other advantages in addition to making available a source of biocidally active materials. For example, these processes offer two separate and distinct novel routes to the synthesis of the cyclic dienic six-membered ring sultones of this invention. Heretofore, only one prior art process was available to prepare six-membered dienic sultone rings. .Fore'xample, the structure where A, B, D and E (which may be'the same or different) are selected from the group consisting of hydrogen and alkyl, have been prepared hitherto only by the reaction of unsaturated ketones with sulfuric acid in the presence of acetic'anhydride. ..However, the prior art process would appear to be limited to the preparation of those sultones having an alkyl group on the carbon atom adjacent to the ring oxygen. Furthermore, the prior art process is severely limited in commercial applicability by the general commercial unavailability of a, B-or ,8, '7- unsatu'rated ketones, with only a few exceptions. Another shortcoming of the prior art process is the neces- GED and compounds of the formula A (my where A, B, C and D (which maybe the same or different) are selected from the group consisting of hydrogen, halogen and alkyl (and where two or more are alkyl, said alkyls being optionally conjoined to forma ring), where G is selected from the group consisting of hydrogen and halogen, and where Y and Z (which may be the same or different) are chosenrfrom the group consisting of halogen, hydroxy, and acyloxy, said compound being reacted with a reagent chosen from the group consisting of concentrated sulfur acid, oleum, and sulfuric anhy dride, said reaction being conducted by admixture at about to 150 degrees centigrade.

The present invention consists in its process aspect of the reaction of at least one compound chosen from the group described by the general formula and where X, G, Y and Z areas defined above, with a reagent chosen from the group consisting of substantially anhydrous H 50 oleum, and sulfuric anhydride. The preferred embodiment is where X equals chlorine and G equals hydrogen or chlorine, and where Y and Z are chosen from the group consisting of chlorine, hydroxy, and acetoxy, which is an organic carbonyloxy, and where the other reagent is ole-um.

Thus, for example, suitable reactants are:

xpense (DI/L II C 12 at: l

10 cmooowmmon; o CHzCl Cl 0 CHBr Hick Cl -"CH2 CHzO C OCH(CH3)=CH:

01 onion 01 v l co 01 01120 G OCH(OH:)=OH2 o1 or n CClz Cl C CH2OCOCH; CHzO C 0 0011 C1 CHzCl CHzOOOCoH;

1 Ci: l =CH2 I CO1: Cl

In regard to the sulfur-containing reagent, oleum (i.e. sulfuric acid containing free S0 is preferred. Also usable are sulfuric.acid, sulfuric acid plus a dehydration, agent suchias P 0 or sulfuric anhydride, or complexes of sulfuric anhydride with various Lewis bases such as dioxane, ethyl ether, pyridine, or the like.

The above reactions are carried out in the liquid phase by admixing one or more of the reactants with the sul-, fonating reagent present in molar excess at temperatures C CHzI CHzOC OCHa C=O Cl GHzOH sluggish at the lower temperature range while at tempera,

tures toward 150 degrees centigrade and above there is, some tendency for undesired and competing side reactions including, sulfonation and/or oxidation of the product, The precise optimum; operating temperature is largely dependent upon the reactivity of the particular aliphatic reactant used. The time will normally be a few minutes to several hours. Isolation of the sultone product may be made through a variety of means including precipitating the product through adding the reaction mixture to water," or by extraction with a sulfuric acid-stable organic sol-; vent, followed by evaporation and crystallization, or by freezing the crystals out. A most convenient isolation ranging from about -20 degrees centigrade to procedure is dilution with water, followed by filtration of the crude product or extraction of the .precipitated crude product by means of a solvent.

In respect to pesticidal use, the preferred method of employing the novel sultones of this invention is to apply the compounds or a formulation thereof to the site of the crop to be protected or to the soil, seeds, roots, foliag branches or fruit. While the precise rates of application depend upon the type and degree of infestation and the tolerance of the plant and the part of the plant treated, rates of from 0.1 to 10 pounds per acre will generally be suitable in foliar application, lower rates in seed application down to 1 ounce per acre, with higher rates, up to above 100 pounds per acre in soil application. While the emphasis in this application has been primarily that of fungicidal treatment of plants, the compounds of this invention used serves equally well as an antimicrobial agents in wood, paper, cloth, leather, stored food products, pulp, plastics and other substances suitable to deterioration due to microorganisms, and will generally be used at 0.1 p.p.m. or higher, in the medium to be treated. The compounds also have utility in paints, varnishes, and other coatings for prevention of attack by fungi, mildew, marine fouling organisms, and the like. The following additional examples are submitted to more clearly illustrate the workings of this invention. Except as indicated in the claims, none of the submitted exemplification is to be construed as limitations of this invention in its composition and process aspects,

EXAMPLE l.--PREPARATION OF C H O Cl S SUL- TONE FROM l,4,5,6,7,7 HEXACHLORO 2,3 BIS (CHLOROMETHYL)BICYCLO(2.2.1) HEPTADI- ENE-2,5

A mixture of 20 parts of 1,2,3,4,7,7-hexachloro-5,6-bis- (chloromethyhbicyclo(2.2.1)-heptadiene-2,5 (prepared as in United States Patent 2,951,098) and 75 parts of oleum (20% S content) is warmed at 75 degrees centigrade for one-half hour. The resultant clear solution is poured with agitation into water at zero to 10 degrees centigrade (approximately 1000 parts). The precipitated solid is removed by filtration and, after washing with water to remove adhering acid, and drying, the solid is recrystallized from hot heptene to obtain 18 parts of colorless crystalline solid, melting point 130 degrees centigrade.

Analysis. Calcd. for C H O Cl -S: C, 26.9; H, 0.50; i

Cl, 52.9; S, 7.94. Found: C, 26.84; H, 0.55; Cl., 52.8; S, 7.99.

The infrared spectrum provides evidence for the -OSO -group as well as two vinylic hydrogen-to-carbon bonds CH structures). Molecular weight calcd. 405; found (ebullioscopic in benzene), 388 (i-l0%).

EXAMPLE 2.-PREPARATION OF 0 11 0 01 SUL- TONE FROM 1,4,5,6,7,7 HEXACHLORO 2,3-BIS (METHYLENE)BICYCLO(2.2.1)-HEPTENE-5 A mixture of parts of 1,4,5,6,7,7-hexachloro-2,3-bis- (methylene)bicyclo(2.2.1)-heptene-5 (J. Am. Chem. Soc. 81, 5415) and 75 parts of oleum (20% S0 is mixed, and spontaneously heated to 40 to 50 degrees centigrade. After 30 minutes, the product is isolated and recrystallized as in Example 1, to obtain 5 parts of colorless product, melting point 130 degrees Centigrade, which by its infrared spectrum is identified to be the same as the product of Example 1.

EXAMPLE 3.-PREPARATION OF C H O Cl S SUL- TONE FROM 1,4,5,6,7,7-HEXACH.LORO 2,3 BIS (HYDROXYMETHYDBICYCLO(2.2.1) HEPTADI- ENE-2,5 A mixture of '10 parts of 1,4,5,6,7,7-hexachloro-2,3-bis (hydroxymethyl)bicyclo(2.2.1) heptad'iene 2,5 (I. Am.

Chem. Soc. 81, 5416) and 75 parts of oleum (20% 80,)

are stirred together, causing an exotherm to 50 degrees centigrade. After 3 hours, the product is isolated and recrystallized as in Example 1, to obtain 5 parts of a product and infrared spectrum.

6 which is the same as in the above examples, by melting point and infrared specturm.

EXAMPLE 4.PREPARATION OF C H O Cl S SUL- TONE FROM 1,4,5,6,7,7 HEXACHLORO 2,3 BIS(ACETOXYMETHYL)BICYCLO(2.2.1) HEP- TADIENE-2,5

EXAMPLE 5.PREPARATION OF C H O Cl S SUL- TONE FROM HEXACHLORO-2-METHYLENE-3- CHLOROMETHYLENE) BICYCLO (2.2.1 HEP- TENE-S A mixture of 5 parts of 1,4,5 ,6,7,7-hexachloro-2-methylene-3 (chloromethylene) bicyclo(2.2.1)-heptene-5 (prepared by dehydrochlorination of 1,4,5,6,7,7-hexachloro-2, 3-bis'(chloromethyl)bicyclo(2.2.1)-heptadiene-2,5 by KOH in CH OH at reflux) plus 12.5 parts of oleum (20% S0 was heated for 30 minutes at 80 degrees Centigrade, then the product isolated and purified as in Example 1, giving a nearly quantitative yield of the sulfone (C H O Cl S, identical in melting point and infrared-spectrum to that made in Example 1.

EXAMPLE 6.--USE OF 65% OLEUM Twenty parts of 1,4,5,6,7,7'- hexachloro 2,3 bis (chloromethyl)bicyclo(2.2.l)-heptadiene and 80 parts of oleum (65% S0 were mixed at room temperature, causing an exothermto 60 degrees centigrade. When the exotherm subsided, the solution was poured slowly into water, and the product isolated by extraction using chloroform, the chloroform evaporated, and the crude product purified as in the preceding examples, to obtain 12 parts of the sultone C H Cl SO identified by melting point EXAMPLE 7.-USE OF SULFURIC ANHYDRIDE Twenty parts of 1,4,5,6,7,7 hexachloro 2,3- bis- (chloromethyl)bicyclo(2.2.1)-heptadiene-2,5- was dissolved in parts of liquid sulfur trioxide (commercial stabilized Sulfan), with cooling to hold the temperature below 50 degrees centigrade. After 10 minutes, the solu tion was cautiously added to crushed ice, and the product extracted from the aqueous-organic mixture by means of chloroform. On evaporation of the chloroform, '21 syrup was obtained which, on dissolving in heptane and chilling the resultant solution, yielded 7 parts of the crystalline sultone C H Cl SO identified by infrared spectrum and melting point. 7

EXAMPLE 8. USE OF SULFURIC ACID Three parts of 1,4,5,6,7,7-hexachloro-2-rnethylene-3- (chloromethylene)bicyclo(2.2.1) heptene 5 and thirtyfive parts of essentially pure sulfuric acid (made by addingsulfuric anhydride in an amount equivalent to the Water present in technical ninety-six percent sulfuric acid), are heated at seventy degrees forone hour, then poured into water. The precipitated solids are filtered off and found to be the sultone C H O Cl S by infrared analysis.

EXAMPLE 9.-EMULSIFIABLE FORMULATION An emulsifiable formulation of the compound 7 .C H O Cl S (prepared as above) is made by blending the following ingredients:

Parts C H O Cl S 1.0 Emcol SOOX (commercial polyoxyethylene-sulfonate emulsifier) 0.3 Emcol 30OX (commercial polyoxyethylene-sulfonate 8 EXAMPLE 'l4.-FUNGICIDAL USE Spore germination tests are carried out by the standard method'of the American Phytopathological Society, employing Alternaria oleracia and Monolinia fructicola as test organisms. Maneb (manganous ethylenbis(dithiocarbamate), a highly effective commercial fungicide,

emulsifier 0.3 was tested for comparison. The results are as follows:

Percent germination of spores at concentrations (p.p.m.) indicated Compound Fungus Cpl-11050158 0 0 U 11 59 82 100 100 100 CaH:O; Gl S 0 0 2 36 42 68 100 100 Maneb 0 0 72 100 100 100 100 100 Maneb U 0 100 100 100 100 100 100 Xylene Q. 6.4 EXAMPLE 15.MITICIDAL ACTIVITY Isophorone Bean plants are sprayed with an aqueous emulsion con- This formulation is emulsified with water prior to spraying.

EXAMPLE 10.DUST FORMULATION A dust formulation of C H O Cl S is made by grinding together the following:

Parts Attapulgus clay 95 C H O Cl S This formulation is applied to crops from a dusting apparatus.

EXAMPLE 1 1.-WETTABLE POWDER A wettable powder formulation of C H O CI S is made by grinding together the following materials:

Parts C H O CI S 1 Microcel E (synthetic silicate) 0.90 Marasperse N (lignin sulfonate dispersant) 0.05 vSorbit P (alkylarylsulfonate wetting agent) 0.05

This formulation is dispersed in water prior to spraying.

EXAMPLE 12.FUNGIOIDAL USE follows:

Percent Concentration of CgH O 'CI S: control 100 p.p.m. 100 50 p.p.m. 100 p.p.m. 98 12.5 p.p.m. 80

EXAMPLE l3.FUNGICIDAL USE Similar tests to the above were run using tomato plants infested with Phytophthora infestans, the causative organism of late blight disease. The following percentages of control were observed:

Percent Concentration of C H O CI S: control 100 p.p.m. 100 50 p.p.m. 99 25 p.p.m. 94

' taining 0.1 percent of C H O Cl -S sultone, and then in- 'fested with T etranyclzus atlanticus mites. Unsprayed control plants are similarly infested. After 5 days, substantially 100 percent kill of mites on the treated plants was observed.

I claim:

1. A compound of the formula X OH X I 7| OX2 SE02 X CH wherein X is selected from the group consisting of chlorine, fluorine and bromine.

01 CH C] I \O I GIG]: S10 01 I 01 on 3. A process for preparing a compound of the formula rine, fluorine, and bromine, which comprises reacting a starting material selected from the group consisting of a compound of the formula X X =ono I 0X, X l =CH:

and a compound of the formula Iii wherein X is selected from the group consisting of chlo- CHzY CHzZ consisting of chlorine, fluorine, bromine and hydrogen, and Y and Z are selected from the group consisting of chlorine, fluorine, bromine, hydroxy and organic carbonyloxy, with a reagent selected from the group consisting of concentrated sulfuric acid, oleurn, and sulfuric anhydride.

rine, fluorine, and bromine, G is selected from the group i 9 i ,7. 10 4. The process of claim 3 in which X is a chlorine sub- 2,958,624 11/ 1960 Bimber 16733 stituent. -1 2,983,732 5/ 1961 Geering et a1 260-327 5. Th 4 h' G l t f e process of claim in w ieh 1s se cc ed rom OTHER REFERENCES the group consisting of hydrogen and chlorine and Y and Z are selected from the group consisting of chlorine, 5 Mustafia: Chem. Reviews, vol. 54, No. 2, pages 195-197 hydroxy substituents and acetoxy substituents. (1954).

6. The process of claim 5 in which the sulfuric acid WALTER A. MQPANCE, Primary Examiner.

material reactant is oleum. IRVING MARCUS, NICHOLAS S. RIZZO,

References Cited by the Examiner 10 JOHN RANDOLPH, Examiners. UNITED STATES PATENTS J. T. MILLER, JAMES A. PATTEN, 2,861,919 11/1958 Gilbert 167-33 L Assistant Examinem 2,900,393 8/1959 Broderick 260-327

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3686419A (en) * 1968-01-23 1972-08-22 Philips Corp Pesticidal composition and method of preparing same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2861919A (en) * 1956-11-13 1958-11-25 Allied Chem Fungicide comprising mucochloric anhydride
US2900393A (en) * 1956-12-11 1959-08-18 Rohm & Haas Preparation of 3-methyl 1,3-propane sultone
US2958624A (en) * 1958-04-30 1960-11-01 Diamond Alkali Co Method of controlling insect and fungi comprising contacting with a 1, 4-diformyl-2, 5-dimethyl piperazine
US2983732A (en) * 1958-05-07 1961-05-09 Hooker Chemical Corp Process for the preparation of organic cyclic sulfites

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2861919A (en) * 1956-11-13 1958-11-25 Allied Chem Fungicide comprising mucochloric anhydride
US2900393A (en) * 1956-12-11 1959-08-18 Rohm & Haas Preparation of 3-methyl 1,3-propane sultone
US2958624A (en) * 1958-04-30 1960-11-01 Diamond Alkali Co Method of controlling insect and fungi comprising contacting with a 1, 4-diformyl-2, 5-dimethyl piperazine
US2983732A (en) * 1958-05-07 1961-05-09 Hooker Chemical Corp Process for the preparation of organic cyclic sulfites

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3686419A (en) * 1968-01-23 1972-08-22 Philips Corp Pesticidal composition and method of preparing same

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